U.S. patent number 9,771,467 [Application Number 14/721,293] was granted by the patent office on 2017-09-26 for thermoplastic resin composition and article comprising the same.
This patent grant is currently assigned to Lotte Advanced Materials Co., Ltd.. The grantee listed for this patent is Samsung SDI Co., Ltd.. Invention is credited to Sung Hee Ahn, Su Hak Bae, Hyun Joo Han, Joong In Kim, Ji Hye Lee, Min Jeong Lee, Ha Na Ra.
United States Patent |
9,771,467 |
Han , et al. |
September 26, 2017 |
**Please see images for:
( Certificate of Correction ) ** |
Thermoplastic resin composition and article comprising the same
Abstract
A thermoplastic resin composition includes a thermoplastic resin
comprising a polycarbonate resin; inorganic fillers; and a
sulfonate represented by Formula 1: ##STR00001## wherein R.sub.1 is
a C.sub.6 to C.sub.30 hydrocarbon group. The thermoplastic resin
composition can have excellent impact resistance, rigidity, flame
retardance, physical property balance therebetween, and the
like.
Inventors: |
Han; Hyun Joo (Uiwang-si,
KR), Lee; Ji Hye (Uiwang-si, KR), Kim;
Joong In (Uiwang-si, KR), Ra; Ha Na (Uiwang-si,
KR), Bae; Su Hak (Uiwang-si, KR), Ahn; Sung
Hee (Uiwang-si, KR), Lee; Min Jeong (Uiwang-si,
KR) |
Applicant: |
Name |
City |
State |
Country |
Type |
Samsung SDI Co., Ltd. |
Yongin-si |
N/A |
KR |
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Assignee: |
Lotte Advanced Materials Co.,
Ltd. (Yongin-si, KR)
|
Family
ID: |
54701008 |
Appl.
No.: |
14/721,293 |
Filed: |
May 26, 2015 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20150344670 A1 |
Dec 3, 2015 |
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Foreign Application Priority Data
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May 30, 2014 [KR] |
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10-2014-0066567 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08K
3/34 (20130101); C08K 3/013 (20180101); C08K
5/42 (20130101); C08K 5/521 (20130101); C08K
5/42 (20130101); C08L 69/00 (20130101); C08K
5/521 (20130101); C08L 69/00 (20130101); C08K
3/013 (20180101); C08L 69/00 (20130101) |
Current International
Class: |
C08K
3/34 (20060101); C08K 5/521 (20060101); C08K
5/42 (20060101) |
Field of
Search: |
;524/127 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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1860145 |
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Nov 2007 |
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EP |
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10-1367088 |
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Dec 2008 |
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KR |
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10-2012-0002991 |
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Jan 2012 |
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KR |
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Other References
Office Action in counterpart Korean Application No. 10-2014-0066567
dated Oct. 13, 2016, pp. 1-5. cited by applicant.
|
Primary Examiner: Lee; Doris
Attorney, Agent or Firm: Additon, Higgins & Pendleton,
P.A.
Claims
What is claimed is:
1. A thermoplastic resin composition comprising: a thermoplastic
resin comprising a polycarbonate resin; inorganic fillers
comprising talc or a combination of talc and wollastonite in an
amount of from about 25 part by weight to about 43 parts by weight
based on about 100 parts by weight of the thermoplastic resin; and
a sulfonate represented by Formula 1 in an amount of from about 0.2
parts by weight to about 0.7 part by weight based on about 100
parts by weight of the thermoplastic resin: ##STR00005## wherein
R.sub.1 is a dodecyl phenyl group wherein thermoplastic resin
composition has a flexural modulus of from about 30,000
kgf/cm.sup.2 to about 100,000 kgf/cm.sup.2 measured according to
ASTM D790, an Izod impact strength of from about 5 kgfcm/cm to
about 15 kgfcm/cm measured on an about 1/8'' thick specimen
according to ASTM D256, and a falling dart impact (FDI) strength of
from about 10 J to about 60 J measured on an about 3.2 mm thick
specimen according to a DuPont drop measurement method.
2. The thermoplastic resin composition according to claim 1,
wherein the talc fillers have an average thickness from about 30 nm
to about 700 nm, an average particle size from about 0.65 .mu.m to
about 5.0 .mu.m, and a ratio of average diameter to average
thickness (diameter/thickness) from about 4 to about 30; and the
wollastonite fillers have an average diameter (D) from about 0.3
.mu.m to about 15 .mu.m, an average length (L) from about 3 .mu.m
to about 3000 .mu.m, and a ratio of the average length to the
average diameter (L/D) from about 10 to about 200.
3. The thermoplastic resin composition according to claim 1,
further comprising at least one of coupling agents, flame retardant
aids, lubricants, plasticizers, heat stabilizers, anti-dripping
agents, antioxidants, photostabilizers, pigments, and dyes.
4. The thermoplastic resin composition according to claim 1,
wherein: the inorganic fillers consist of talc.
5. The thermoplastic resin composition according to claim 1,
wherein the inorganic fillers comprise a mixture of talc and
wollastonite.
6. The thermoplastic resin composition according to claim 5,
wherein the mixture of talc and wollastonite comprises talc in an
amount of about 60 to about 99 wt %.
7. The thermoplastic resin composition according to claim 1,
wherein the thermoplastic resin comprises polycarbonate resin and
optionally another resin that is not the same as the polycarbonate
resin in an amount of about 1 to about 30 wt %, based on the total
weight of the thermoplastic resin.
8. The thermoplastic resin composition according to claim 7,
wherein the other resin that is not the same as the polycarbonate
resin is a polyester resin.
9. The thermoplastic resin composition according to claim 1,
further comprising about 1 part by weight to about 25 parts by
weight of a flame retardant based on about 100 parts by weight of
the thermoplastic resin.
10. The thermoplastic resin composition according to claim 9,
wherein the flame retardant is a phosphorus flame retardant.
11. The thermoplastic resin composition according to claim 10,
wherein the thermoplastic resin has a flame retardance rating of
V-0 determined using five 1.2 mm thick bars according to UL 94
inflammability test standard.
12. A molded article produced from the thermoplastic resin
composition according to claim 1.
13. The molded article according to claim 12, wherein the molded
article is a housing for an electronic device having a thickness of
from about 0.5 to about 3.0 mm.
Description
CROSS-REFERENCE TO RELATED APPLICATION
This application claims priority under 35 USC Section 119 to and
the benefit of Korean Patent Application No. 10-2014-0066567, filed
May 30, 2014, the entire disclosure of which is incorporated herein
by reference.
FIELD OF THE INVENTION
The present invention relates to a thermoplastic resin composition,
and a molded article comprising the same.
BACKGROUND
If a thermoplastic or thermosetting resin is blended with inorganic
fillers such as glass fibers, silica, talc and the like, the resin
can exhibit improved stiffness, such as tear strength, tensile
strength, flexural strength, flexural modulus and the like, due to
inherent properties of the inorganic fillers. Typically, a blend of
the thermoplastic resins such as polycarbonates, and the like with
the inorganic fillers has been used for molded articles requiring
high stiffness, especially, as interior materials and exterior
materials of vehicles, electric appliances, and electronic
devices.
However, when the thermoplastic resin is blended with the inorganic
fillers, the thermoplastic resin can suffer from deterioration in
fluidity (moldability) and deterioration in appearance, such as
protrusion of the inorganic fillers from a surface of a molded
article, and the like. To solve such problems, a material capable
of controlling interface properties between the thermoplastic resin
and the fillers is typically used. Such materials include
surfactants, coupling agents and the like, and the interface
properties can be controlled in a manner in which one side of the
material acts on the thermoplastic resin and the other side thereof
acts on the fillers. If the interface properties are controlled,
the resin can exhibit improved impact strength, fluidity, and the
like.
US Patent Publication No. 2012-0245262 discloses a polycarbonate
composition using a sulfonate and inorganic fillers to improve
impact properties thereof. EP 1860145 discloses a polysulfone
composition using fibrous (acicular) fillers and a sulfonate to
improve impact properties thereof.
As such, although the thermoplastic resin can exhibit improved
stiffness, impact resistance and the like using the inorganic
fillers, the coupling agent and the like, an excess of inorganic
fillers can cause the resin to be easily broken at room temperature
and it can be difficult to prevent deterioration in elongation,
fluidity and the like. In addition, it can be difficult to improve
stiffness of the resin despite use of the coupling agent and a
compatibilizer, unlike properties such as impact resistance,
fluidity and the like.
Therefore, there is a need for a thermoplastic resin composition
that exhibits excellent stiffness, excellent impact resistance, and
the like.
SUMMARY
The present invention provides a thermoplastic resin composition
that can have excellent impact resistance, stiffness, flame
retardance, and the like, and a molded article comprising the
same.
In exemplary embodiments, the thermoplastic resin composition
comprises a thermoplastic resin comprising a polycarbonate resin;
inorganic fillers; and a sulfonate represented by Formula 1:
##STR00002##
wherein R.sub.1 is a C.sub.6 to C.sub.30 hydrocarbon group.
In exemplary embodiments, the inorganic fillers may be flake
fillers, acicular fillers, or a mixture thereof.
In exemplary embodiments, the flake fillers may be talc, mica, or a
mixture thereof, and the acicular fillers may be wollastonite,
whisker, glass fibers, basalt fibers, or a mixture thereof.
In exemplary embodiments, the flake fillers may have an average
thickness from about 30 nm to about 700 nm, an average particle
size from about 0.65 .mu.m to about 5.0 .mu.m, and a ratio of
average diameter to average thickness (diameter/thickness) from
about 4 to about 30; and the acicular fillers may have an average
diameter (D) from about 0.3 .mu.m to about 15 .mu.m, an average
length (L) from about 3 .mu.m to about 3000 .mu.m, and a ratio of
the average length to the average diameter (L/D) from about 10 to
about 200.
In exemplary embodiments, the inorganic fillers may be present in
an amount of from about 1 part by weight to about 80 parts by
weight based on about 100 parts by weight of the thermoplastic
resin, and the sulfonate may be present in an amount of from about
0.1 parts by weight to about 1.0 part by weight based on about 100
parts by weight of thermoplastic resin.
In exemplary embodiments, the thermoplastic resin composition may
further comprise about 1 part by weight to about 25 parts by weight
of a flame retardant based on about 100 parts by weight of the
thermoplastic resin.
In exemplary embodiments, the flame retardant may be a phosphorus
flame retardant.
In exemplary embodiments, the thermoplastic resin composition may
further comprise at least one of coupling agents, flame retardant
aids, lubricants, plasticizers, heat stabilizers, anti-dripping
agents, antioxidants, photostabilizers, pigments, and dyes.
In exemplary embodiments, the inorganic fillers may be a mixture of
the flake fillers and the acicular fillers.
In exemplary embodiments, the thermoplastic resin composition may
have a flexural modulus of from about 30,000 kgf/cm.sup.2 to about
100,000 kgf/cm.sup.2 measured according to ASTM D790, an Izod
impact strength of from about 5 kgfcm/cm to about 15 kgfcm/cm
measured on an about 1/8'' thick specimen according to ASTM D256,
and a falling dart impact (FDI) strength of from about 10 J to
about 60 J measured on an about 3.2 mm thick specimen according to
a DuPont drop measurement method.
The present invention also relates to a molded article produced
from the thermoplastic resin composition.
In exemplary embodiments, the molded article may be a housing for
an electronic device having a thickness of from about 0.5 mm to
about 3.0 mm.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a .sup.1H-NMR spectrum of aluminum dodecyl benzene
sulfonate prepared in Preparative Example 1.
DETAILED DESCRIPTION
Exemplary embodiments now will be described more fully hereinafter
in the following detailed description, in which some, but not all
embodiments of the invention are described. Indeed, this invention
may be embodied in many different forms and should not be construed
as limited to the embodiments set forth herein; rather, these
embodiments are provided so that this disclosure will satisfy
applicable legal requirements.
A thermoplastic resin composition according to the present
invention can have improved impact resistance and stiffness such as
flexural modulus, and the like, and comprises (A) a thermoplastic
resin comprising a polycarbonate resin; (B) inorganic fillers; and
(C) a sulfonate represented by Formula 1.
(A) Thermoplastic Resin
According to the present invention, the thermoplastic resin may
include a polycarbonate resin, and the polycarbonate resin may be
used alone, or in combination with another thermoplastic resin that
is not the same as the polycarbonate resin.
The polycarbonate resin may be a typical thermoplastic
polycarbonate resin. For example, the polycarbonate resin may be an
aromatic polycarbonate resin prepared by reacting one or more
diphenols (aromatic diol compounds) with a precursor such as
phosgene, halogen formates, carbonic acid diesters, and the
like.
Examples of diphenols may include without limitation 4,4'-biphenol,
2,2-bis(4-hydroxyphenyl)propane,
2,4-bis(4-hydroxyphenyl)-2-methylbutane,
1,1-bis(4-hydroxyphenyl)cyclohexane,
2,2-bis(3-chloro-4-hydroxyphenyl)propane,
2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, and the like, and
combinations thereof. For example, the diphenol may include
2,2-bis(4-hydroxyphenyl)propane,
2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, and/or
1,1-bis(4-hydroxyphenyl)cyclohexane, for example
2,2-bis(4-hydroxyphenyl)propane, which is also referred to as
bisphenol-A.
The polycarbonate resin may be a branched polycarbonate resin and
may be prepared by, for example, reacting about 0.05 mol % to about
2 mol % of a polyfunctional compound containing tri- or higher
functional groups, for example, tri- or higher-valent phenol
groups, based on the total amount of diphenols used in
polymerization.
The polycarbonate resin may be used in the form of a
homo-polycarbonate resin, a co-polycarbonate resin, or blends
thereof.
In addition, the polycarbonate resin may be partially or completely
replaced by an aromatic polyester-carbonate resin obtained by
polymerization in the presence of an ester precursor, for example,
a bifunctional carboxylic acid.
The polycarbonate resin may have a weight average molecular weight
(Mw) from about 10,000 g/mol to about 200,000 g/mol, for example,
from about 15,000 g/mol to about 40,000 g/mol, without being
limited thereto.
Furthermore, the polycarbonate resin may have a melt flow index of
from about 5 g/10 min to about 50 g/10 min, for example from about
5 g/10 min to about 30 g/10 min at a temperature of about
300.degree. C. under about 1.2 kg according to ISO 1133. Within
this range, the thermoplastic resin composition may have excellent
impact resistance, stiffness, and the like.
As the other thermoplastic resin that is not the same as the
polycarbonate resin, a typical thermoplastic resin such as a
polyester resin, an aromatic vinyl resin, a polyphenylene ether
resin, an acrylic resin, a polyamide resin, a polyolefin resin, and
the like, and combinations thereof may be used. In exemplary
embodiments, polyester resin may be used.
A suitable polyester resin used typically in the thermoplastic
resin composition, without limitation, may be used as the polyester
resin. The polyester resin may be prepared by polycondensing a
dicarboxylic acid compound and a diol compound, and the
polycondensation can be easily practiced by those skilled in the
art.
Examples of the dicarboxylic acid compound may include without
limitation terephthalic acid (TPA), isophthalic acid (IPA),
1,2-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic
acid, 1,5-naphthalene dicarboxylic acid, 1,6-naphthalene
dicarboxylic acid, 1,7-naphthalene dicarboxylic acid,
1,8-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic
acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene
dicarboxylic acid, alkyl esters of the foregoing, such as dimethyl
terephthalate (hereinafter DMT, an aromatic dicarboxylate with an
acid substituted with a dimethyl group, and the like), dimethyl
isophthalate, alkylester of naphthalene dicarboxylic acid, such as
dimethyl-1,2-naphthalate, dimethyl-1,5-naphthalate,
dimethyl-1,6-naphthalate, dimethyl-1,7-naphthalate,
dimethyl-1,8-naphthalate, dimethyl-2,3-naphthalate,
dimethyl-2,6-naphthalate, and/or dimethyl-2,7-naphthalate, and the
like, and mixtures thereof.
Examples of the diol compound may include without limitation
C.sub.2 to C.sub.12 diols, for example, ethylene glycol,
1,2-propylene glycol, 1,3-propylene glycol,
2,2-dimethyl-1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol,
1,5-pentanediol, 1,5-pentanediol, 1,6-hexanediol,
1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and the like,
and mixtures thereof.
In exemplary embodiments, the polyester resin may have a melt flow
index of from about 5 g/10 min to about 50 g/10 min, for example,
from about 5 g/10 min to about 30 g/10 min at a temperature of
about 300.degree. C. under about 1.2 kg according to ISO 1133.
Within this range, the thermoplastic resin composition may have
excellent impact resistance, stiffness, and the like.
In exemplary embodiments, if the thermoplastic resin in addition to
the polycarbonate resin such as the polyester resin, and the like
is used, it may be present in an amount of from about 1 wt % to
about 30 wt %, for example, from about 5 wt % to about 25 wt %
based on the total weight (100 wt %) of the thermoplastic resin. In
some embodiments, the mixture or combination of polycarbonate resin
and the other thermoplastic resin may include the other
thermoplastic resin in an amount of about 1, 2, 3, 4, 5, 6, 7, 8,
9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25,
26, 27, 28, 29, or 30 wt %. Further, according to some embodiments
of the present invention, the amount of the other thermoplastic
resin can be in a range from about any of the foregoing amounts to
about any other of the foregoing amounts.
Within this range, the thermoplastic resin composition may have
excellent scratch resistance, flexural modulus, abrasion
resistance, and the like.
(B) Inorganic Fillers
According to the present invention, the inorganic fillers may
include typical flake (lamella-type) fillers and/or acicular
(needle-type) fillers. Examples of flake fillers may include talc,
mica, and the like, and mixtures thereof, for example, talc,
without being limited thereto. Examples of the acicular fillers may
include wollastonite, whiskers, glass fibers, basalt fibers, and
the like, and mixtures thereof, for example, wollastonite and
whiskers, without being limited thereto.
In exemplary embodiments, the wollastonite may be a hydrophobic
surface treated wollastonite, and examples of the whiskers may
include without limitation potassium titanate whiskers, magnesium
sulfate whiskers, calcium carbonate whiskers, aluminum borate
whiskers, and the like, and mixtures thereof. In addition, the
glass fibers may include a glass fiber reinforcing agent in which
fibers are formed by bundling glass filaments coated with a sizing
agent, such as epoxy, urethane, and/or silane, without being
limited thereto. Herein, the sizing agent may be present in an
amount of about 0.05 parts by weight to about 0.1 parts by weight
based on about 100 parts by weight of the glass filaments, without
being limited thereto.
In exemplary embodiments, the flake fillers have a thin film shape
having a small z-axis length (thickness) as compared with a
sectional area formed by x-axis and y-axis lengths. In addition,
the flake fillers may have an average thickness from about 30 nm to
about 700 nm, for example, from about 30 nm to about 300 nm, and as
another example from about 32 nm to about 270 nm; an average
particle size from about 0.65 .mu.m to about 5.0 .mu.m, for
example, from about 0.65 .mu.m to about 2.7 .mu.m, and as another
example from about 0.8 .mu.m to about 2.5 .mu.m; and a ratio of an
average diameter (average x-axis and y-axis lengths) to the average
thickness (z-axis length) (aspect ratio, diameter/thickness) from
about 4 to about 30, for example, from about 10 to about 30. As the
ratio of the average diameter to average thickness increases,
stiffness of the thermoplastic resin composition improves.
For reference, the average particle size of the flake fillers
refers to a median value of particle size distribution measured by
X-ray transmission. Specifically, the particle size distribution of
the flake fillers are obtained by X-ray transmission of sinking
particles, followed by calculating the median value, thereby
obtaining the average particle size.
In addition, the acicular fillers have an acicular (fibrous) shape,
and may have an average diameter (D) from about 0.3 .mu.m to about
15 .mu.m, for example, from about 0.5 .mu.m to about 13 .mu.m, an
average length (L) from about 3 .mu.m to about 3,000 .mu.m, for
example, from about 5 .mu.m to about 2,600 .mu.m, and a ratio of
the average length to the average diameter (aspect ratio, L/D) from
about 10 to about 200, for example, from about 20 to about 100.
Within this range, the thermoplastic resin composition can exhibit
shrinkage stability, high stiffness, and the like.
The thermoplastic resin composition may include the inorganic
fillers in an amount of about 1 part by weight to about 80 parts by
weight, for example, about 5 parts by weight to about 50 parts by
weight, and as another example about 10 parts by weight to about 40
parts by weight, based on about 100 parts by weight of the
thermoplastic resin. In some embodiments, the thermoplastic resin
composition may include the inorganic fillers in an amount of about
1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19,
20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36,
37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53,
54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70,
71, 72, 73, 74, 75, 76, 77, 78, 79, or 80 parts by weight. Further,
according to some embodiments of the present invention, the amount
of inorganic fillers can be in a range from about any of the
foregoing amounts to about any other of the foregoing amounts.
Within this range, the thermoplastic resin composition can exhibit
excellent impact resistance, stiffness, and the like.
In exemplary embodiments, when the flake fillers and the acicular
filler are used together, the flake fillers may be present in an
amount of about 1 wt % to about 99 wt %, for example, about 10 wt %
to about 70 wt %, and as another example about 10 wt % to about 60
wt % based on the total amount (total weight, 100 wt %) of the
inorganic fillers, and the acicular fillers may be present in an
amount of about 1 wt % to about 99 wt %, for example, about 30 wt %
to about 90 wt %, and as another example about 40 wt % to about 90
wt % based on a total amount (total weight, 100 wt %) of the
inorganic fillers.
In some embodiments, the mixture or combination of flake fillers
and the acicular filler may include the flake fillers in an amount
of about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17,
18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34,
35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51,
52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68,
69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85,
86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99 wt %.
Further, according to some embodiments of the present invention,
the amount of flake fillers can be in a range from about any of the
foregoing amounts to about any other of the foregoing amounts.
In some embodiments, the mixture or combination of flake fillers
and the acicular filler may include the acicular fillers in an
amount of about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15,
16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32,
33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49,
50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66,
67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83,
84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99
wt %. Further, according to some embodiments of the present
invention, the amount of acicular fillers can be in a range from
about any of the foregoing amounts to about any other of the
foregoing amounts.
Within this range, the thermoplastic resin composition can exhibit
excellent impact resistance, stiffness, and the like.
(C) Sulfonate
According to the present invention, the sulfonate serves to control
interface properties between the inorganic fillers and the
thermoplastic resin and disperse the fillers in the resin, and may
be represented by the following Formula 1:
##STR00003##
wherein R.sub.1 is a C.sub.6 to C.sub.30 hydrocarbon group, for
example, a C.sub.6 to C.sub.30 alkyl group, a C.sub.7 to C.sub.30
arylalkyl group or a C.sub.7 to C.sub.30 alkylaryl group, for
example a C.sub.12 to C.sub.18 hydrocarbon group (alkyl group,
arylalkyl group, alkylaryl group, and the like).
Examples of the sulfonate may include aluminum
dodecylbenzenesulfonate, aluminum octadecylbenzenesulfonate,
aluminum decylsulfonate, aluminum octadecylsulfonate, and the like,
and mixtures thereof, without being limited thereto.
The sulfonate may be prepared by a typical process of producing the
sulfonate, for example, but not limited to, the preparation in the
Preparative Example 1 below.
The thermoplastic resin composition may include the sulfonate in an
amount of about 0.1 parts by weight to about 1.0 part by weight,
for example, about 0.3 parts by weight to about 0.7 parts by
weight, based on about 100 parts by weight of the thermoplastic
resin. In some embodiments, the thermoplastic resin composition may
include the sulfonate in an amount of about 0.1, 0.2, 0.3, 0.4,
0.5, 0.6, 0.7, 0.8, 0.9, or 1.0 part by weight. Further, according
to some embodiments of the present invention, the amount of
sulfonate can be in a range from about any of the foregoing amounts
to about any other of the foregoing amounts.
Within this range, the thermoplastic resin composition can exhibit
excellent impact resistance, stiffness, and the like.
According to the present invention, the thermoplastic resin
composition may further comprise a flame retardant to improve flame
retardance.
The flame retardant may include typical flame retardant used in
thermoplastic resin compositions. For example, phosphorus flame
retardant may be used. Examples of the phosphorus flame retardants
may include without limitation red phosphorus, a phosphate
compound, a phosphonate compound, a phosphinate compound, a
phosphine oxide compound, a phosphazene compound, a metal salt
thereof, and the like. The phosphorus flame retardant may be used
alone or in admixture of two or more thereof. In exemplary
embodiments, the aromatic phosphoric acid ester compound
represented by the following Formula 2 may be used as the
phosphorus flame retardant:
##STR00004##
wherein, R.sub.2, R.sub.3, R.sub.5 and R.sub.6 are the same or
different and are each independently a hydrogen atom, a
C.sub.6-C.sub.20 aryl group, or a C.sub.6-C.sub.20 aryl group
substituted with a C.sub.1-C.sub.10 alkyl group, R.sub.4 is a
C.sub.6-C.sub.20 arylene group or a C.sub.6-C.sub.20 arylene group
substituted with a C.sub.1-C.sub.10 alkyl group, for example, those
derived from dialcohol such as resorcinol, hydroquinone,
bisphenol-A, bisphenol-S, and the like, and n is an integer of from
0 to 4.
The examples of the aromatic phosphoric acid ester compound
represented by Formula 2 may include, if n is 0, for example,
diaryl phosphate such as diphenyl phosphate, and the like,
triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate,
tri(2,6-dimethylphenyl)phosphate,
tri(2,4,6-trimethylphenyl)phosphate,
tri(2,4-di-tert-butylphenyl)phosphate, and the like, and if n is 1,
for example, bisphenol A bis(diphenyl phosphate), resorcinol
bis(diphenyl phosphate), resorcinol
bis[bis(2,6-dimethylphenyl)phosphate], resorcinol b is
[bis(2,4-di-tert-butylphenyl)phosphate], hydroquinone
bis[bis(2,6-dimethylphenyl)phosphate], hydroquinone
bis[bis(2,4-di-tert-butylphenyl)phosphate], and the like. The
aromatic phosphoric acid ester compound may be used alone or in
admixture of two or more thereof.
If the flame retardant is used, then it may be present in an amount
of from about 1 part by weight to about 25 parts by weight, for
example, from about 10 to about 15 parts by weight based on about
100 parts by weight of the thermoplastic resin. In some
embodiments, the thermoplastic resin composition may include the
flame retardant in an amount of about 1, 2, 3, 4, 5, 6, 7, 8, 9,
10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25
parts by weight. Further, according to some embodiments of the
present invention, the amount flame retardant can be in a range
from about any of the foregoing amounts to about any other of the
foregoing amounts.
Within this range, the thermoplastic resin composition may have
excellent flame retardance with minimal or no degradation of impact
resistance, stiffness, and the like.
According to the present invention, the thermoplastic resin
composition may further comprise, as necessary, one or more
additives used typically the thermoplastic resin composition such
as a coupling agent such as a silane coupling agent, and the like,
flame retardant aids, lubricants, plasticizers, heat stabilizers,
anti-dripping agents, antioxidants (oxidation stabilizer),
photostabilizers, pigments, dyes, and the like. These may be used
alone or in admixture of two or more thereof.
In exemplary embodiments, the additives may be present, but not
limited to, in an amount of from about 0.1 parts by weight to about
10 parts by weight based on about 100 parts by weight of the
thermoplastic resin.
The thermoplastic resin composition of the present invention may
have a form of the pellet prepared by mixing and melt extruding the
components using a typical twin screw extruder at a temperature of
from about 200.degree. C. to about 280.degree. C., for example,
from about 250.degree. C. to about 260.degree. C.
The pellet may be prepared into a number of molded articles through
a number of molding processes such as an injection molding, an
extrusion molding, a vacuum molding, a casting molding, and the
like. The molding processes are well known to those skilled in the
art.
In exemplary embodiments, the thermoplastic resin composition of
the present invention may have a flexural modulus from about 30,000
kgf/cm.sup.2 to about 100,000 kgf/cm.sup.2, for example, from about
50,000 kgf/cm.sup.2 to about 80,000 kgf/cm.sup.2, according to ASTM
D790.
The thermoplastic resin composition may have an Izod impact
strength of from about 5 kgfcm/cm to about 15 kgfcm/cm, for
example, from about 6 kgfcm/cm to about 10 kgfcm/cm, measured on an
about 1/8'' thick specimen according to ASTM D256.
In addition, the thermoplastic resin composition may have a falling
dart impact (FDI) strength (crack generation energy) from about 10
J to about 60 J, for example, from about 15 J to about 40 J, as
measured on an about 1 mm thick specimen (about 10 cm.times.about
10 cm.times.about 1 mm) using an about 2 kg dart in accordance with
the Dupont drop measurement method, in which a maximum height not
generating a crack is measured by adjusting a height of the dart,
followed by converting the maximum height into potential energy.
Here, the maximum height not generating a crack is obtained in such
a manner that a dart having a certain weight is dropped onto the
about 1 mm thick specimen from a varying height, followed by
observing generation of cracks in the specimen by the naked
eye.
A molded article according to the present invention may be prepared
from the polycarbonate resin composition through a number of
molding processes, and may have excellent stiffness, impact
resistance, flame retardance, physical property balance
therebetween, and the like. Moreover, the molded article may be
used for an electrical/electronic product, an interior/exterior
material of a vehicle, and the like requiring high stiffness and
high impact properties, for example, a housing for an electronic
device (a thin film type exterior material) having a thickness of
about 0.5 mm to about 3.0 mm.
Hereinafter, the present invention will be described in more detail
with reference to the following Examples. However, it should be
understood that these examples are provided for illustration only
and the scope of the present invention is not limited to the
following Examples. Details not described herein that can be
inferred sufficiently and technically from the present invention by
those skilled in the art are omitted.
EXAMPLES
Preparative Example 1
Preparation of Sulfonate
350 g of dodecyl benzene sulfonic acid is dissolved in 300 mL of
ethanol while heating to a temperature of 40.degree. C., and to the
solution 70 g of aluminum isopropoxide is slowly added, stirred and
heated. The solution is reacted for 3 hours while heating to about
80.degree. C. and maintaining this temperature, and the reactants
are allowed to cool to the ambient temperature and filtered to
remove the impurities. A vacuum distillation unit is used to remove
ethanol and the resulting isopropyl alcohol from the solution in
which the impurities are removed, and prepare aluminum dodecyl
benzene sulfonate. The prepared aluminum dodecyl benzene sulfonate
may be used as a 50-80% diluted alcoholic solution, or as a vacuum
dried powder. The decision on whether the reaction of aluminum
dodecyl benzene sulfonate is completed is made by comparing the
isopropoxide proton shift of the reactants and the product by a
1H-NMR spectrum (see FIG. 1). In addition, a thermal gravimetric
analysis (TGA) and an inductively coupled plasma (ICP) are used to
calculate the content of aluminum dodecyl benzene sulfonic acid in
the reaction solution. The analysis results of ICP of the product
are shown in Table 1.
TABLE-US-00001 TABLE 1 Sample weight (g) 0.106 Diluent weight(g)
109.904 Ion content Al 19578.9 (mg/kg) Ca N.D. Mg N.D. Na N.D. Zn
N.D. N.D.: None Detected
Hereinafter, the components of Examples and Comparative Examples
are as follows.
(A) Thermoplastic Resin
(A-1) Polycarbonate Resin
Bisphenol-A polycarbonate (Manufacturer: Cheil Industries Inc.,
Trade name: PC-03-SC-1190G, melt flow index (MI, measured at
300.degree. C. under 1.2 kg according to ISO 1133): 30 g/10 min) is
used.
(A-2) Polyester Resin
Polybutylene terephthalate (Manufacturer: SHINKONG, Trade name:
Shinite K001, melt flow index (MI, measured at 240.degree. C. under
1.0 kg according to ISO 1133): 18 g/10 min) is used.
(B) Inorganic Filler
(B-1) Flake filler: Talc (Manufacturer: KOCH Co., Ltd., Trade name:
KC-3000) is used.
(B-2) Acicular filler: Wollastonite (Manufacturer: NYCO Co., Ltd.,
Trade name: 4W) is used.
(C) Sulfonate
(C-1) Aluminum dodecyl benzene sulfonate of Preparative Example 1
is used.
(C-2) Sodium dodecyl benzene sulfonate (Manufacturer: TCI, Trade
name: D0990) is used.
(C-3) Potassium dodecyl benzene sulfonate (Manufacturer: Geo-Young
Corporation, Trade name: DBC70M) is used.
(D) As a calcium salt, calcium stearate (CA-ST, Manufacturer:
Songwon Industrial Co., Ltd., Trade name: SC-110) is used.
(E) Flame retardant: A mixture of the phosphorus flame retardant (a
mixture of CR-741 and PX-200 from DAIHACHI Chemical Industry Co.,
Ltd., mixing ratio (weight ratio) of 19:1) is used.
Examples 1 to 14 and Comparative Examples 1 to 10
Pellets are prepared by adding the components in the amounts as
shown in Tables 2 and 5 and extruding at a temperature of 200 to
280.degree. C. A twin screw extruder with L/D=36 and a diameter of
45 mm is used to carry out the extrusion, and the prepared pellets
are dried at 100.degree. C. for 4 hours or more and injected in a 6
ounce injector (molding temperature of 260.degree. C. and mold
temperature of 60.degree. C.) to prepare a specimen. The prepared
specimen is evaluated for the physical properties according to the
following method, and the results thereof are shown in Tables 2 to
5.
Evaluation of Properties
(1) Izod impact strength (unit: kgfcm/cm): Izod impact strength is
measured on a 1/8'' thick notched Izod specimen in accordance with
ASTM D256.
(2) Falling dart impact (FDI) strength (unit: J): FDI strength is
measured by measuring a height for generating a crack in a 1.0 mm
thick specimen (10 cm.times.10 cm.times.1 mm) using a 2 kg dart in
accordance with the Dupont drop measurement method, followed by
converting the height into energy.
(3) Flexural modulus (unit: kgf/cm.sup.2): Flexural modulus is
determined at 2.8 mm/min according to ASTM D790.
(4) Flame retardance: Flame retardance is determined using five 1.2
mm thick bars according to UL 94 inflammability test standard.
TABLE-US-00002 TABLE 2 Comparative Examples Examples 1 2 3 4 5 1 2
3 4 Composition (A-1) (pbw) 100 100 100 100 100 100 100 100 100
(B-1) (pbw) 25 25 25 25 25 25 25 25 25 (C) (C-1) 0.2 0.3 0.4 0.5
0.7 -- -- -- -- (pbw) (C-2) -- -- -- -- -- -- 0.5 -- -- (C-3) -- --
-- -- -- -- -- 0.5 -- (D) (pbw) -- -- -- -- -- -- -- -- 0.5
Physical Izod impact 5.2 6.5 7.1 7.5 7.8 3.5 4.4 4.8 3.3 properties
strength FDI strength 10 13 15 20 23 2 7 7 1
TABLE-US-00003 TABLE 3 Examples Comparative Examples 6 5 6 Compo-
(A) (pbw) (A-1) 80 80 80 sition (A-2) 20 20 20 (B-1) pbw) 25 25 25
(C-1) (pbw) 0.5 -- -- (D) (pbw) -- -- 0.5 Physical Izod impact
strength 6.5 4.2 3.2 proper- FDI strength 15 4 2 ties Flexural
modulus 44900 51200 44300
TABLE-US-00004 TABLE 4 Comparative Examples Examples 7 8 9 10 11 12
7 8 Composition (A-1) (pbw) 100 100 100 100 100 100 100 100 (B)
(B-1) 17.6 17.6 17.6 17.6 17.6 14 11.1 11.1 (pbw) (B-2) 11.1 11.1
11.1 11.1 11.1 29 17.6 17.6 (C-1) (pbw) 0.1 0.2 0.3 0.4 0.5 0.5 --
-- (D) (pbw) -- -- -- -- -- -- -- 0.5 Physical properties Izod
impact 7.7 8.5 8.7 9 9.4 8.1 3.9 3.5 strength FDI strength 10 14 20
23 29 21 2 0.5 Flexural 53.6 51.3 50.7 52.4 50.3 63.3 48.0 63.6
modulus (.times.10.sup.3)
TABLE-US-00005 TABLE 5 Examples Comparative Examples 13 14 9 10
Compo- (A-1) (pbw) 100 100 100 100 sition (B-1) (pbw) 25 25 25 25
(C) (pbw) (C-1) 0.3 0.5 -- -- (C-2) -- -- 0.3 0.5 (E) (pbw) 21 21
21 21 Physical Izod impact strength 9.0 9.8 8.0 8.5 proper- FDI
strength 40 48 44 46 ties Flexural modulus 33000 32000 30900 30600
Flame retardance/ V-0 V-0 V-1 V-1 1.2 mm (total (25) (26) (59)
(109) burning time, s)
The results demonstrate that the thermoplastic resin composition of
the present invention can have excellent Izod impact strength and
FDI strength (impact resistance), stiffness (flexural modulus),
physical property balance therebetween, and the like. Furthermore,
when the flame retardant is used, the results also demonstrate that
the thermoplastic resin composition of the present invention can
have more excellent flame retardance.
Many modifications and other embodiments of the invention will come
to mind to one skilled in the art to which this invention pertains.
Therefore, it is to be understood that the invention is not to be
limited to the specific embodiments disclosed and that such
modifications and other embodiments are intended to be included
within the scope of the appended claims.
* * * * *